JP5942421B2 - Adhesive aid, RFL adhesive treatment liquid and rubber composition-fiber composite - Google Patents

Description

  The present invention relates to an adhesion assistant, an RFL adhesive treatment liquid, and a rubber composition-fiber composite, and in particular, an adhesion assistant that increases the initial adhesion between the rubber composition and the fiber and the adhesion after heat deterioration, The present invention relates to an RFL adhesive treatment liquid and a rubber composition-fiber composite.

  Rubber products such as tires, belts, hoses and air springs are used in fields such as automobile parts, industrial parts and building materials. These products are made from rubber such as natural rubber, styrene butadiene rubber, and chlorosulfonated polyethylene, and rubber compositions containing carbon black, plasticizer, anti-aging agent, vulcanization accelerator, etc. are impregnated with adhesive. -Manufactured as a composite of vulcanized and bonded fibers such as dried polyester fiber, polyamide fiber, and glass fiber.

  Examples of the adhesive that enhances the adhesion between the rubber composition and the fibers include resorcin-formalin condensate solution (RF liquid), and processing liquid in which a rubber latex such as vinylpyridine styrene butadiene copolymer resin latex is mixed with the RF liquid. (RFL liquid), and further, a treatment liquid in which an isocyanate compound, an epoxy compound, or the like is mixed with the RFL liquid is used. These adhesives increase the adhesive strength between rubber and fiber, but with high temperature vulcanization and heat deterioration, auxiliary materials such as vulcanization accelerators and vulcanizing agents in the rubber composition migrate to the fiber, and the rubber composition Deterioration of objects and fibers occurs, and the adhesive force between the rubber composition and the fibers decreases. In order to prevent this, it has been proposed to prevent deterioration by using the following various chlorinated compounds.

  (1) A compound containing a vinyl halide group having a film formation temperature of 200 ° C. or less in the RFL solution, such as vinyl chloride homopolymer, vinyl chloride and vinyl acetate, vinyl chloride and vinylidene chloride, vinyl chloride and acrylonitrile, vinyl chloride The polyester fiber is impregnated and dried with a treatment solution to which a terpolymer of vinyl acetate and maleic anhydride or a mixture thereof is added, and then the rubber composition and the treated fiber are vulcanized and bonded (for example, Patent Documents). 1). This method is excellent in initial adhesive strength and adhesive strength after heat deterioration, but has a problem that initial adhesive strength and thermal adhesive strength are not excellent for fibers other than polyester fibers. Further, there is a problem that the emulsion stability of the RFL adhesive treatment liquid is not excellent.

  (2) Combined use of vinyl chloride copolymer latex and chlorosulfonated polyethylene latex in RF solution, for example, olefins such as vinyl chloride and ethylene, alkyl acrylates such as vinyl chloride and methyl acrylate, vinyl chloride and vinyl acetate, etc. After mixing with vinyl chloride copolymer latex and epoxy compound or blocked isocyanate compound and impregnating and drying in aromatic polyamide fiber, further impregnating and drying in chlorosulfonated polyethylene latex and RF solution, and adding with chlorinated polyethylene rubber. Sulfur bonding is performed (for example, Patent Document 2). This method certainly has excellent initial adhesive strength and heat-resistant adhesive strength, but its effect is limited to chlorinated polyethylene and aromatic polyamide fibers, and does not improve the heat-resistant adhesive properties of other fibers and rubbers.

  (3) An RFL solution is mixed and dispersed in an aqueous solution obtained by synthesizing a resin solution obtained by condensing para-chlorophenol or a derivative thereof, resorcinol and formaldehyde with a large amount of ammonia, and then impregnated and dried with a Tetron fiber. And vulcanized (for example, Patent Document 3). Although this method certainly improves the initial adhesive strength and heat-resistant adhesive strength, its effect is limited to tetron fibers, and there is a problem with the deterioration of the working environment due to volatilization of ammonia and the storage stability of the liquid mixture using this. was there.

JP 2000-234275 A Japanese Patent No. 3765072 Japanese Examined Patent Publication No. 46-11251

  The present invention has been made in view of the above problems, and its purpose is to provide adhesion between various fibers such as tetron fiber, nylon fiber, and glass fiber and various rubber compositions such as natural rubber and styrene butadiene rubber. Another object of the present invention is to provide an adhesion assistant that is excellent in heat-resistant adhesive force between a fiber after heat deterioration and a rubber composition and excellent in emulsion stability of an RFL adhesive treatment solution.

  As a result of intensive studies to solve the above-mentioned problems, the present inventors have found that a specific vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex can solve the above-mentioned problems. It came to complete. That is, the present invention includes a vinyl chloride- (meth) acrylic acid alkyl ester copolymer containing vinyl chloride and a predetermined (meth) acrylic acid alkyl ester, having a pH of 3 to 8 and an average particle size of 0.05 to 1.0 μm. An adhesion aid, an RFL adhesive treatment liquid, and a rubber composition-fiber composite, characterized by containing latex.

  Hereinafter, the present invention will be described in detail.

  The adhesion assistant of the present invention contains a vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex containing vinyl chloride and an alkyl (meth) acrylic acid ester represented by the following general formula (1).

（式中、Ｒ_１は水素又はメチル基を表し、ｎは１〜１０の整数を表す。）
本発明の接着助剤が含有する塩化ビニル−（メタ）アクリル酸アルキルエステル共重合体ラテックスは、ｐＨ３〜８である。ｐＨが３未満又は８を超えると、（メタ）アクリル酸アルキルエステルのエステルが加水分解を受け易く初期及び耐熱劣化後の接着力が損なわれる。

(In the formula, R ₁ represents hydrogen or a methyl group, and n represents an integer of 1 to 10.)
The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contained in the adhesion aid of the present invention has a pH of 3-8. If the pH is less than 3 or exceeds 8, the ester of the (meth) acrylic acid alkyl ester is easily hydrolyzed, and the adhesive strength after the initial stage and after heat resistance deterioration is impaired.

  The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contained in the adhesion aid of the present invention has an average particle size of 0.05 to 1.0 μm. If the average particle size is less than 0.05 μm, the initial and post-heat deterioration adhesive strength is impaired, and if the average particle size exceeds 1.0 μm, the storage stability and rubber of the RFL adhesive treatment liquid mixed and dispersed with the RFL liquid The adhesive strength of the composition-fiber composite is impaired.

  The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex in the vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex provides the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat degradation. In order to further improve and improve the storage stability of the RFL adhesive treatment liquid, the weight ratio of vinyl chloride / (meth) acrylic acid alkyl ester in the copolymer is in the range of 98/2 to 80/20. Is preferred.

  The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contained in the adhesion aid of the present invention further prevents hydrolysis when the adhesion aid of the present invention is mixed and dispersed in the RFL liquid, and is heat resistant. In order to further improve the adhesiveness after deterioration, it is preferable to contain an organic compound having a sulfonate or sulfate ester salt and a higher fatty acid salt.

  Examples of the organic compound having a sulfonate include alkylbenzene sulfonates such as sodium dodecylbenzenesulfonate and ammonium dodecylbenzenesulfonate; dialkylsulfosuccinates such as sodium dioctylsulfosuccinate and sodium dihexylsulfosuccinate; alkylnaphthalenesulfonic acid Examples thereof include alkyl naphthalene sulfonates such as sodium; alkyl diphenyl ether disulfonates such as sodium alkyl diphenyl ether disulfonate. Examples of the organic compound having a sulfate ester salt include alkyl sulfate esters such as sodium lauryl sulfate and sodium myristyl sulfate; polyoxyethylene alkyl sulfate salts, polyoxyethylene alkylaryl sulfate salts, and the like. As content of the organic compound which has a sulfonate or a sulfate ester salt, in order to stabilize latex more, 0.20-10 with respect to 100 weight part of vinyl chloride- (meth) acrylic-acid alkylester copolymers. 0.0 part by weight is preferred.

  Examples of the higher fatty acid salt include salts of lauric acid, myristic acid, palmitic acid, stearic acid, oleic acid and the like with an alkali. From the viewpoint of availability, a salt with sodium, potassium, ammonia, or triethanolamine is preferable. The content of the higher fatty acid salt is preferably 0.05 to 3.0 parts by weight, more preferably 0.1 to 1.0 parts by weight, in order to adjust the pH to 3 to 8.

  The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contained in the adhesion aid of the present invention is a polymerization initiator in order to further stabilize the polymerization or prevent the occurrence of scale, if necessary. , A chain transfer agent, a reducing agent, a pH buffering agent, and the like.

  The vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contained in the adhesion aid of the present invention is a simple substance of a vinyl chloride monomer and a (meth) acrylic acid alkyl ester represented by the following general formula (2). The polymer can be produced, for example, by emulsion polymerization, microsuspension polymerization, seed emulsion polymerization, seed microsuspension polymerization or the like.

（式中、Ｒ_１は水素又はメチル基を表し、ｎは１〜１０の整数を表す。）
塩化ビニル単量体と共重合する上記式（１）で示される（メタ）アクリル酸アルキルエステルの単量体としては、例えば、（メタ）アクリル酸メチル、（メタ）アクリル酸エチル、（メタ）アクリル酸ｎ−ブチル、（メタ）アクリル酸イソ−ブチル、（メタ）アクリル酸ｎ−ペンチル、（メタ）アクリル酸イソ−ペンチル、（メタ）アクリル酸ｎ−ヘキシチル、（メタ）アクリル酸イソ−ヘキシル、（メタ）アクリル酸ｎ−オクチル、（メタ）アクリル酸２−エチル−ヘキシル、（メタ）アクリル酸ｎ−デシル等が好適なものとして挙げられることができ、これらは２種以上でも用いることができる。なお、上記式（１）のｎ＝０では、得られるゴム組成物−繊維複合体の成型体の初期接着力が損なわれ、ｎ＝１１以上では、得られる塩化ビニル−（メタ）アクリル酸アルキルエステル共重合体ラテックスの平均粒子径が１．０μｍを超え、ＲＦＬ接着剤処理液の貯蔵安定性が低下する。

(In the formula, R ₁ represents hydrogen or a methyl group, and n represents an integer of 1 to 10.)
Examples of the monomer of the alkyl (meth) acrylate ester represented by the above formula (1) that is copolymerized with the vinyl chloride monomer include, for example, methyl (meth) acrylate, ethyl (meth) acrylate, (meth) N-butyl acrylate, iso-butyl (meth) acrylate, n-pentyl (meth) acrylate, iso-pentyl (meth) acrylate, n-hexyl (meth) acrylate, iso-hexyl (meth) acrylate , (Meth) acrylic acid n-octyl, (meth) acrylic acid 2-ethyl-hexyl, (meth) acrylic acid n-decyl, and the like may be mentioned as preferred, and these may be used in two or more. it can. When n = 0 in the above formula (1), the initial adhesive strength of the resulting molded rubber composition-fiber composite is impaired, and when n = 11 or more, the resulting vinyl chloride-alkyl (meth) acrylate is obtained. The average particle diameter of the ester copolymer latex exceeds 1.0 μm, and the storage stability of the RFL adhesive treatment liquid is lowered.

  When producing a vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex, an organic compound having a sulfonate salt or a sulfate ester salt and a higher fatty acid salt can be added. The organic compound having a sulfonate or a sulfate ester salt can be added as appropriate before the start of polymerization, during the polymerization, or after the completion of the polymerization. The higher fatty acid salt can be added before the start of polymerization, during the polymerization, or after the completion of the polymerization, and the higher fatty acid salt can be added successively or divided during the polymerization. The organic compound having a sulfonate or sulfate ester salt and the higher fatty acid salt are as described above.

  When producing a vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex, a polymerization initiator for the purpose of initiation of polymerization, a chain transfer agent, a reducing agent for the purpose of stabilizing the polymerization and reducing the amount of scale generated PH buffering agents and the like can be added.

  Examples of the polymerization initiator include water-soluble initiators such as potassium persulfate and ammonium persulfate, 2,2′-azobisisobutyronitrile, 2,2′-azobis-2-methylbutyronitrile, Examples thereof include oil-soluble initiators such as lauroyl peroxide, t-butylperoxypivalate, diacyl peroxide, peroxyester, and peroxydicarbonate.

  Any chain transfer agent may be used as long as it can adjust the degree of polymerization of the vinyl chloride polymer. Examples thereof include halogenated hydrocarbons such as trichloroethylene and carbon tetrachloride; 2-mercaptoethanol, octyl 3-mercaptopropionate, and dodecyl mercaptan. And aldehydes such as acetone and n-butyraldehyde.

  Examples of the reducing agent include sodium sulfite, ammonium sulfite, sodium hydrogen sulfite, ammonium hydrogen sulfite, ammonium thiosulfate, potassium metabisulfite, sodium dithionite, sodium formaldehyde sulfoxylate, L-ascorbic acid, dextrose, Examples thereof include ferrous sulfate and copper sulfate.

  Examples of the pH buffering agent include alkali metal monohydrogen phosphate, alkali metal dihydrogen phosphate, potassium hydrogen phthalate, boric acid-caustic potassium, sodium hydrogen carbonate, and the like.

  The polymerization temperature is not particularly limited, but is preferably 30 to 100 ° C, more preferably 40 to 80 ° C.

  The adhesion aid of the present invention contains, in addition to vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex, an anti-aging agent, an antioxidant, an antiseptic, an antifungal agent, etc., as necessary. Can do.

  The RFL adhesive treatment liquid of the present invention contains the above-mentioned adhesion assistant, an RFL liquid containing an aqueous solution of resorcin and formalin condensate, and rubber latex.

  The aqueous solution of resorcin and formalin condensate contained in the RFL solution is, for example, a resorcin such as 1,3-benzenediol, 1,5-benzenediol, bishydroxymethylphenol, bishydroxyalkylphenol such as bishydroxyethylphenol, and formalin. An aqueous solution of the condensate can be mentioned. These are produced by a basic catalyst such as sodium hydroxide, potassium hydroxide or ammonia, or an acid catalyst such as hydrochloric acid or sulfuric acid.

  The rubber latex contained in the RFL liquid is, for example, a vinylpyridine-styrene-butadiene copolymer latex, a modified latex obtained by modifying a vinylpyridine-styrene-butadiene copolymer latex with a carboxyl group, or a styrene-butadiene copolymer. Latex and its modified latex, acrylonitrile-butadiene rubber and its modified latex, natural rubber latex, chloroprene rubber latex, butyl rubber latex, acrylate copolymer latex, etc. In particular, it is desirable to contain a vinylpyridine-styrene-butadiene copolymer latex.

  The RFL liquid containing an aqueous solution of resorcin and formalin condensate and rubber latex can be obtained by mixing an aqueous solution of resorcin and formalin condensate and rubber latex in an arbitrary ratio.

  The RFL adhesive treatment liquid of the present invention is obtained by mixing and dispersing an adhesion assistant in an RFL liquid containing an aqueous solution of resorcin and formalin condensate and rubber latex. The mixing / dispersing method is not particularly limited, and examples thereof include mixing / dispersing with a stirring blade and mixing / dispersing with a homogenizer.

  The RFL adhesive treatment liquid of the present invention may contain an isocyanate compound, a blocked isocyanate compound, an epoxy compound, or the like as necessary.

  Examples of isocyanate compounds include polyisocyanates such as tolylene diisocyanate, m-phenylene diisocyanate, diphenylmethane diisocyanate, hexamethylene diisocyanate, polymethylene polyphenyl polyisocyanate, or compounds having two or more of these isocyanates and active hydrogen atoms, for example, And polyhydric alcohol-added polyisocyanate compounds obtained by reacting with trimethylolpropane yapentaerythritol and the like.

  Examples of the blocked isocyanate compound include polyisocyanates such as aromatic secondary amines such as diphenylamine and xylidine; phthalimides; lactams such as caprolactam and valerolactam; oximes such as acetoxime, methyl ethyl ketone oxime, and cyclohexaneoxime. Examples thereof include blocked polyisocyanate compounds obtained by reacting a blocking agent such as a kind.

  Although it does not specifically limit as an epoxy compound, It is a polyepoxide compound which has two or more epoxy in a molecule | numerator, for example, polyhydric alcohols, such as ethylene glycol, glycerol, sorbitol, pentaerythritol, polyethyleneglycol, and epichlorohydrin. Reaction products such as halogen-containing epoxides, reaction products of resorcin, bis (4-hydroxyphenyl) dimethylmethane, polyhydric phenols such as phenol / formaldehyde resin and the halogen-containing epoxides, and 3,4-epoxycyclohexene Examples thereof include epoxide, 3,4-epoxycyclohexylmethyl, 3,4-epoxycyclohexenecarboxylate, and bis (3,4-epoxy-6-methyl-cyclomethyl) adipate.

  These isocyanate compounds, blocked isocyanate compounds, and epoxy compounds may be used as fiber treatment agents, and the fibers may be directly diluted with an organic solvent in ethyl acetate or the like, coated and dried, or mixed and dispersed in an RFL adhesive treatment solution. These compounds can be used as they are or after being dissolved in a small amount of a solvent as required, and then mixed with an anionic surfactant such as sodium alkylbenzene sulfonate or a nonionic emulsifier such as polyoxyethylene alkylphenyl ether. You may mix and disperse.

  Examples of the fiber to be treated with the RFL adhesive treatment liquid of the present invention include polyester fiber, nylon fiber, glass fiber, rayon fiber, vinylon fiber, and soot, but are not particularly limited. The shape of the fiber includes various forms such as a thread, a cord, a woven fabric, a nonwoven fabric, a sheet, a short fiber, a film, and a sheet, but is not particularly limited.

  The method of immersing the fiber in the RFL adhesive treatment liquid of the present invention is not particularly limited, but 1) a method of impregnating and drying the fiber of the RFL adhesive treatment liquid of the present invention 2) isocyanate compound, blocked isocyanate A method in which a compound or an epoxy compound is previously diluted in an organic solvent such as ethyl acetate and immersed and dried in a fiber, and then the fiber is impregnated and dried with the RFL adhesive treatment liquid of the present invention. 3) Isocyanate compound, blocked isocyanate compound or epoxy compound Can be mixed and dispersed in the RFL adhesive treatment solution of the present invention and impregnated and dried into fibers.

  The fiber impregnated with the RFL adhesive treatment liquid of the present invention is subjected to a drying process for removing moisture at 80 to 150 ° C., and is then used to promote resinification of the RFL adhesion treatment liquid and chemical bonding with the fiber. Although it is preferable to perform heat treatment (baking) at a temperature of 0 ° C. or higher, there is no particular limitation on the baking method. In addition, the fiber which does not need to perform a baking process does not need to perform this process.

  The rubber composition used in the rubber composition-fiber composite of the present invention is a raw material rubber and a secondary raw material comprising a filler, a plasticizer, a vulcanizing agent, a vulcanization accelerator, an antiaging agent, a processing aid and the like. It is a rubber compound obtained by kneading a product.

  The raw rubber is not particularly limited, but is an unsaturated rubber such as natural rubber (NR), styrene butadiene rubber (SBR), nitrile butadiene rubber (NBR), chloroprene rubber (CR), butyl rubber, halogenated butyl rubber, Examples include chlorosulfonated polyethylene (CSM), chlorinated polyethylene, hydrogenated nitrile rubber, ethylene propylene rubber, epichlorohydrin rubber, saturated rubber such as fluoro rubber, acrylic rubber, and silicone rubber. You may use together the rubber | gum of a seed | species or more.

  For example, in addition to fillers such as carbon black, mica, silica, clay, magnesium hydroxide, aluminum hydroxide, graphite, mica and ferrite, the auxiliary raw materials are paraffinic oil, naphthenic oil, aroma oil, soybean oil Vegetable oils such as rapeseed oil, phthalates such as dibutyl phthalate and dioctyl phthalate, plasticizers such as liquid rubber such as liquid butadiene rubber, vulcanizing agents such as sulfur and benzoyl peroxide, tetramethylthiuram disulfide, tetraethyl Vulcanization accelerators such as thiuram disulfide, morpholinodithiobenzothiazole, diphenylthiourea, diphenylguanidine, mercaptobenzothiazole, N-sulfenamide, zinc dimethyldicarbamate, and metal oxides such as magnesium oxide and lead oxide Accelerator, scorch inhibitor such as phthalic anhydride, nitrosodiphenylamine, anti-aging agent such as N-isopropyl N′-phenyl-p-phenylenediamine, 2,6-di-t-butylcatechol, mercaptobenzimidazole, thio Peptizers such as xylenol and dixyl disulfide, active agents such as wax and stearic acid, tackifiers such as terpene phenol, gum rosin and tall oil rosin, sodium bicarbonate, azodicarbonamide, p, p'-oxybis ( Examples thereof include foaming agents such as benzenesulfonyl hydrazide, and there are no particular restrictions on the use of these.

  The kneading of the raw rubber and the auxiliary raw material is not particularly restricted but is mixed and dispersed by a mixer such as an open roll, a pressure kneader, or a Banbury mixer.

  When the form of the fiber is a cord, a woven fabric, a sheet, etc., for example, the fiber is baked after being dipped in the RFL adhesive treatment liquid of the present invention that enhances the adhesion between the rubber composition and the fiber and dried to remove moisture. The fiber that needs to be treated is a fiber that has been subjected to a baking treatment) and the rubber composition, and the rubber composition is vulcanized to simultaneously bond the rubber composition and the fiber. You can get a body. When the fiber is short fiber, for example, the rubber composition is immersed in the RFL adhesive treatment liquid of the present invention, dried short fibers are kneaded and vulcanized to obtain a rubber composition. The rubber composition-fiber composite of the present invention can be obtained by simultaneously bonding the fiber and the fiber. Examples of the vulcanization method include press vulcanization, steam vulcanization, hot air vulcanization, UHF vulcanization, electron beam vulcanization, and molten salt vulcanization, and any method may be used.

  The molded article of the rubber composition-fiber composite of the present invention can be obtained by molding the above-described rubber composition-fiber composite of the present invention. Examples of the molding method include calendering, extrusion molding, injection molding, and compression molding, and these are not particularly limited.

  The RFL adhesive treatment liquid of the present invention in which the adhesion assistant of the present invention is mixed and dispersed in the RFL liquid is excellent in storage stability and work environment, and is impregnated into a fiber and then dried to obtain a rubber composition of the present invention. The object-fiber composite is excellent in the initial adhesive force between the rubber composition and the fiber and the adhesive force after heat deterioration.

  The present invention will be described more specifically with reference to the following examples and comparative examples, but the present invention is not limited to these examples.

  In addition, the evaluation method of the fiber treatment liquid and rubber composition-fiber composite in the following Examples and Comparative Examples is as follows.

<Measurement method of pH>
Using a pH meter (trade name D-12, manufactured by Horiba, Ltd.), the pH of the vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex was measured at room temperature without adjusting the concentration.

<Measurement method of average particle diameter>
The average particle size of the vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex was determined by using a particle size distribution analyzer (Microtrac UPA150, manufactured by Nikkiso Co., Ltd.) and setting the refractive index of the dispersion medium to 1.33. The diameter distribution was measured, the median particle diameter was determined, and the average particle diameter of each resin particle was obtained.

<Storage stability of RFL adhesive treatment liquid>
25.0 g of the RFL adhesive treatment solution was placed in a 30 ml sample bottle and allowed to stand at room temperature (23 ° C.) for 1 week, and the presence or absence of sediment was evaluated as follows.

    ○: No sediment is generated.

    Δ: Slight occurrence was observed.

    X: A large amount of sediment was observed.

<Measurement of initial adhesive strength of rubber composition-fiber composite>
A sheet of the rubber composition-fiber composite that was left in a temperature-controlled room (25 ° C., relative humidity 65%) for 1 day or longer was made into a strip-shaped test piece having a width of 25 mm and a length of 100 mm or more in accordance with JISK6502. The test piece was subjected to a peel test between the vulcanized rubber composition and the fiber at a peel rate of 50 mm / min using a tensile tester (Orientec Co., Ltd., Model RTM-500) to determine the peel strength, and the initial adhesive strength and did.

<Measurement of adhesive strength of rubber composition-fiber composite after heat resistance deterioration>
The rubber composition-fiber composite sheet was post-vulcanized at 175 ° C. for 2 hours in a gear oven, and the peel test of the rubber composition-fiber composite sheet was performed in the same manner as the initial adhesive strength, after heat resistance deterioration The adhesive strength was.

Example 1
As shown in Table 1, 670.0 g of deionized water, 540.0 g of vinyl chloride monomer, 60.0 g of butyl acrylate monomer, and 3% by weight potassium persulfate aqueous solution as an initial charge in a 2.5 L autoclave 5.4 g and 50.0 g sodium dodecylbenzenesulfonate aqueous solution having a concentration of 5% by weight were charged, the temperature was raised to 66 ° C., and emulsion polymerization was started. The temperature was kept at 66 ° C., and 60 minutes after the start of the polymerization, 130.0 g of 5 wt% sodium dodecylbenzenesulfonate aqueous solution and 46.0 g of 5 wt% potassium laurate aqueous solution were continuously added over 240 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.7 MPa, unreacted vinyl chloride monomer and butyl acrylate monomer were recovered. To this was added 56.4 g of 5 wt% aqueous sodium dodecylbenzenesulfonate solution and 21.6 g of 5 wt% aqueous potassium laurate solution to obtain an adhesion assistant (vinyl chloride / butyl acrylate copolymer latex) (pH 6). .7, average particle size 0.12 μm).

実施例２〜３
表１に示す通り、実施例１と同様の操作で、アクリル酸ブチル単量体の替わりにアクリル酸メチル単量体（実施例２）、アクリル酸２−エチルへキシル単量体（実施例３）を共重合成分とし、接着助剤（塩化ビニル／アクリル酸メチル共重合体ラテックス、塩化ビニル／アクリル酸２−エチルヘキシル共重合体ラテックス）を各々得た（ｐＨ及び平均粒子径を表１に示す）。

Examples 2-3
As shown in Table 1, in the same manner as in Example 1, methyl acrylate monomer (Example 2), 2-ethylhexyl acrylate monomer (Example 3) instead of butyl acrylate monomer ) Was used as a copolymer component, and adhesion aids (vinyl chloride / methyl acrylate copolymer latex, vinyl chloride / 2-ethylhexyl acrylate copolymer latex) were obtained (pH and average particle diameter are shown in Table 1). ).

Examples 4-5
As shown in Table 1, in the same manner as in Example 1, 670.0 g of deionized water, 540.0 g of vinyl chloride monomer, and 60.0 g of butyl acrylate monomer were charged into a 2.5 L autoclave. The amount of aqueous sodium dodecylbenzenesulfonate solution was changed to obtain an adhesion assistant (vinyl chloride / butyl acrylate copolymer latex) (pH and average particle size are shown in Table 1).

Example 6
<Preparation of RF solution>
16.6 g of resorcin, 14.7 g of formalin 37% aqueous solution (dry weight 5.4 g), 1.3 g of sodium hydroxide and 334.4 g of water were dissolved in a 0.5 liter beaker, and the mixture was heated at room temperature (25 ° C.) for 2 hours. After stirring and condensing using a magnetic stirrer, 366.0 g of RF liquid having a resin solid content of 6.4% by weight was obtained.

<Preparation of RFL solution>
Solid content, RF solution 36.0g and polyvinyl pyridine styrene butadiene rubber 100.0g RF liquid 366.0g and polyvinyl pyridine styrene butadiene rubber latex (Nippon Zeon, Nipol 2518GL) 250.0g The mixture was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours while stirring to obtain 616.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesion assistant (vinyl chloride / vinyl chloride / sodium chloride) were used so that the solid content was 100.0 parts by weight of RFL resin and 20.0 parts by weight of the vinyl chloride / butyl acrylate copolymer prepared in Example 1. 22.3 g of butyl acrylate copolymer latex) was placed in a 0.5 liter beaker, aged for 10 minutes while stirring with a magnetic stirrer, and then 2.1 parts by weight of VALQUABOND MDX (manufactured by Across Chemical Co.) as an isocyanate compound. .3 g was added and stirred for 20 minutes, followed by filtration through a 100 mesh wire netting to prepare an RFL adhesive treatment solution having a solid content concentration of 21% by weight.

<Treatment with RFL Adhesive Treatment Solution (Preparation of Tetron Fiber)>
Tetron cloth (Shikishima canvas, T-81) is immersed in the RFL adhesive treatment solution for 10 minutes, dried in a 140 ° C gear oven, and then subjected to a pressureless baking process for 2 minutes on an electric heat press at 240 ° C. And treated with an RFL adhesive treatment solution.

<Preparation of rubber composition>
Natural rubber was used as a raw rubber, and a natural rubber composition was prepared with a 12-inch roll by the following composition.

Natural rubber 100.0 parts by weight Zinc flower 5.0
Stearic acid 2.0
FEF carbon black 45.0
Process oil 5.0
N-oxydiethylene-2-benzothiazylsulfenamide 1.0
Sulfur 2.5
2,2,4-Trimethyl-1,2-dihydroquinoline polymer 1.0
1,3-diphenylguanidine 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching a tetron fiber treated with an RFL adhesive treatment solution with a natural rubber composition and press vulcanizing at 150 ° C. for 30 minutes. Thereafter, it was left in a thermostatic chamber (25 ° C., relative humidity 65%) for 1 day or longer, and the initial adhesive strength was measured. The adhesive strength after heat resistance deterioration was measured after the rubber composition-fiber composite was placed in an oven at 175 ° C. The results are shown in Table 2. As is apparent from Table 2, the RFL adhesive treatment liquid is excellent in storage stability, and the obtained rubber composition-fiber composite (natural rubber composition-tetron fiber composite) has an initial adhesive strength and after heat deterioration. Adhesive strength was excellent.

実施例７〜８
実施例６と同様にして、表２に示すとおりの実施例２〜３で調製した接着助剤（塩化ビニル／アクリル酸メチル共重合体ラテックス、塩化ビニル／アクリル酸２−エチルヘキシル共重合体ラテックス）を用いたＲＦＬ接着剤処理液、ゴム組成物−繊維複合体を調製し、評価した。その結果を表２に示す。表２から明らかなように、ＲＦＬ接着剤処理液は貯蔵安定性に優れ、得られたゴム組成物−繊維複合体（天然ゴム組成物−テトロン繊維複合体）の初期接着力や耐熱劣化後の接着力が優れていた。

Examples 7-8
In the same manner as in Example 6, adhesion promoters prepared in Examples 2 to 3 as shown in Table 2 (vinyl chloride / methyl acrylate copolymer latex, vinyl chloride / 2-ethylhexyl acrylate copolymer latex) An RFL adhesive treatment solution and a rubber composition-fiber composite were prepared and evaluated. The results are shown in Table 2. As is apparent from Table 2, the RFL adhesive treatment liquid is excellent in storage stability, and the obtained rubber composition-fiber composite (natural rubber composition-tetron fiber composite) has an initial adhesive strength and after heat deterioration. Adhesive strength was excellent.

Examples 9-10
In the same manner as in Example 6, RFL adhesive treatment liquid, rubber composition-fiber composite using adhesion assistants (vinyl chloride / butyl acrylate copolymer latex) having different particle diameters prepared in Examples 4 to 5 The body was prepared and evaluated. The results are shown in Table 2. As is apparent from Table 2, the RFL adhesive treatment liquid is excellent in storage stability, and the obtained rubber composition-fiber composite (natural rubber composition-tetron fiber composite) has an initial adhesive strength and after heat deterioration. Adhesive strength was excellent.

Example 11
<Preparation of rubber composition>
A styrene-butadiene rubber (SBR) was used as a raw rubber, and an SBR composition was prepared with a 12-inch roll by the following composition.

SBR (JSR1502, manufactured by JSR) 100.0 parts by weight Zinc flower 3.0
Stearic acid 2.0
FEF carbon black 85.0
Process oil 20.0
N-oxydiethylene-2-benzothiazylsulfenamide 1.0
Sulfur 1.5
2,2,4-Trimethyl-1,2-dihydroquinoline polymer 1.0
1,3-diphenylguanidine 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching a tetron fiber treated with an RFL adhesive treatment solution with an SBR composition, press vulcanized at 150 ° C. for 30 minutes, and evaluated in the same manner as in Example 6. The results are shown in Table 2. As is clear from Table 2, the RFL adhesive treatment solution is excellent in storage stability, and the obtained rubber composition-fiber composite (SBR composition-tetron fiber composite) has an initial adhesive strength and adhesion after heat deterioration. The power was excellent.

Example 12
<Preparation of rubber composition>
A chloroprene rubber (CR) was used as a raw rubber, and a CR composition was prepared with a 12-inch roll by the following composition.

CR (R-10, manufactured by Tosoh Corporation) 100.0 parts by weight Zinc flower 5.0
Magnesium oxide 4.0
Stearic acid 1.5
FEF carbon black 40.0
Dioctyl adipate bis (2-ethylhexyl) 5.0
Octylated diphenylamine 2.0
N, N′-diphenyl-p-phenylenediamine 0.35
<Preparation of rubber composition-fiber composite>
A rubber composition-fiber composite was prepared by sandwiching a tetron fiber treated with an RFL adhesive treatment solution with a CR composition, press vulcanized at 150 ° C. for 30 minutes, and evaluated in the same manner as in Example 6. The results are shown in Table 3. As is apparent from Table 3, the RFL adhesive treatment solution is excellent in storage stability, and the resulting rubber composition-fiber composite (CR composition-tetron fiber composite) has an initial adhesive strength and adhesion after heat deterioration. The power was excellent.

実施例１３
＜ゴム組成物の調製＞
クロロスルホン化ポリエチレンゴム（ＣＳＭ）を原料ゴムとし、以下の配合によりＣＳＭ組成物を１２インチロールで調製した。

Example 13
<Preparation of rubber composition>
Chlorosulfonated polyethylene rubber (CSM) was used as a raw rubber, and a CSM composition was prepared with a 12-inch roll by the following composition.

CSM (Ectos (registered trademark) T1010, manufactured by Tosoh Corporation) 100.0 parts by weight Magnesium oxide 4.0
Stearic acid 1.5
SRF carbon black 40.0
Pentaerythritol 3.0
Dipentamethylene disulfide 0.2
<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by immersing a dismodule RE (manufactured by Sumitomo Bayer), which is an isocyanate compound, in a 5% solution diluted with ethyl acetate and drying Tetron fiber dried at 140 ° C. as a resin solid content. The Tetron fiber treated with the RFL adhesive treatment solution so as to be 100.0 parts by weight of RFL resin and 20.0 parts by weight of the vinyl chloride / butyl acrylate copolymer prepared in Example 1 was sandwiched with the CSM composition. It was prepared by press vulcanization at 150 ° C. for 30 minutes and evaluated in the same manner as in Example 6. The results are shown in Table 3. As is apparent from Table 3, the RFL adhesive treatment solution is excellent in storage stability, and the obtained rubber composition-fiber composite (CSM composition-tetron fiber composite) has an initial adhesive strength and adhesion after heat deterioration. The power was excellent.

Examples 14-17
<Preparation of RF solution>
Resorcin 11.0 g, formalin 37% aqueous solution 16.2 g (dry weight 6.0 g), sodium hydroxide 0.3 g and water 235.8 g were dissolved in a 0.5 liter beaker and heated at room temperature (25 ° C.) for 6 hours. After stirring and condensing using a magnetic stirrer, 266.0 g of RF liquid having a resin solid content of 6.5% by weight was obtained.

<Preparation of RFL solution>
266.0 parts by weight of RF solution and polyvinylpyridine / styrene / butadiene rubber latex (Nipol 2518FS, manufactured by Nippon Zeon Co., Ltd.) 247. The solid content is RF 17.3 g and polyvinylpyridine / styrene / butadiene rubber 100.0 g. 0 g and 74.0 g of water were added, and the mixture was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours with stirring to obtain 587.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesion assistant (vinyl chloride / vinyl chloride / sodium chloride) were used so that the solid content was 100.0 parts by weight of RFL resin and 20.0 parts by weight of the vinyl chloride / butyl acrylate copolymer prepared in Example 1. 22.3 g of butyl acrylate copolymer latex) was placed in a 0.5 liter beaker and aged for 30 minutes while stirring with a magnetic stirrer to prepare an RFL adhesive treatment solution having a solid concentration of 21% by weight.

<Treatment with RFL adhesive treatment solution (preparation of nylon fibers)>
Nylon cloth (Shikishima Canvas Co., Ltd., N-856) is immersed in the RFL adhesive treatment solution for 10 minutes, dried in a 140 ° C gear oven, and then subjected to a pressureless baking process on a 190 ° C electric heat press for 2 minutes. And treated with an RFL adhesive treatment solution.

<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching RFL adhesive-treated fibers with a natural rubber composition, an SBR composition, a CR composition, and a CSM composition, respectively, and press vulcanizing at 150 ° C. for 30 minutes. Evaluation was performed in the same manner as in Example 6. The results are shown in Table 3. As is apparent from Table 3, the RFL adhesive treatment liquid is excellent in storage stability, and the resulting rubber composition-fiber composite (natural rubber composition-nylon fiber composite, SBR composition-nylon fiber composite, The initial adhesive strength of the CR composition-nylon fiber composite and the CSM composition-nylon fiber composite) and the adhesive strength after heat resistance deterioration were excellent.

Examples 18-21
<Preparation of RFL solution>
Solid solution, RF solution 366.0g and polyvinyl pyridine styrene butadiene rubber latex (Nipol 2518GL, manufactured by Nippon Zeon Co., Ltd.) so that RF 23.3 parts by weight and polyvinyl pyridine styrene butadiene rubber 100.0 parts by weight 250.0 g was placed in a beaker equipped with a 1 liter stirrer and aged for about 20 hours with stirring to obtain 616.0 g of RFL solution having a solid content concentration of 20% by weight.

<Preparation of RFL adhesive treatment liquid>
200.0 g of RFL solution and an adhesion assistant (vinyl chloride / vinyl chloride / sodium chloride) were used so that the solid content was 100.0 parts by weight of RFL resin and 20.0 parts by weight of the vinyl chloride / butyl acrylate copolymer prepared in Example 1. 22.3 g of butyl acrylate copolymer latex) was placed in a 0.5 liter beaker, aged for 10 minutes while stirring with a magnetic stirrer, and then 2.1 parts by weight of VALQUABOND MDX (manufactured by Across Chemical Co.) as an isocyanate compound. .3 g was added and stirred for 20 minutes, followed by filtration through a 100 mesh wire netting to prepare an RFL adhesive treatment solution having a solid content concentration of 21% by weight.

<Treatment with RFL adhesive treatment solution (preparation of glass fiber)>
A glass fiber cloth (manufactured by Kanebo Co., Ltd., KS4300UNT) was immersed in an RFL adhesive treatment solution for 10 minutes and then dried in a gear oven at 140 ° C. to obtain a treated fiber using the RFL adhesive treatment solution.

<Preparation of rubber composition-fiber composite>
The rubber composition-fiber composite was prepared by sandwiching RFL adhesive-treated fibers with a natural rubber composition, an SBR composition, a CR composition, and a CSM composition, respectively, and press vulcanizing at 150 ° C. for 30 minutes. Evaluation was performed in the same manner as in Example 6. The results are shown in Table 4. As is apparent from Table 4, the RFL adhesive treatment liquid is excellent in storage stability, and the resulting rubber composition-fiber composite (natural rubber composition-glass fiber composite, SBR composition-glass fiber composite, The initial adhesive strength of the CR composition-glass fiber composite and the CSM composition-glass fiber composite) and the adhesive strength after heat resistance deterioration were excellent.

比較例１
１ｍ^３オートクレーブ中に脱イオン水３６０．０ｋｇ、塩化ビニル単量体３００．０ｋｇ、過酸化ラウロイル１０．０ｋｇ、１５重量％ドデシルベンゼンスルホン酸ナトリウム水溶液３０．０ｋｇ及びドデシルメルカプタン１．５ｋｇを仕込み、該重合液をホモジナイザーにより２時間循環し、均質化処理を行った後、温度を４５℃に挙げて重合反応を開始した。圧力が低下した後、未反応塩ビ単量体を回収し、平均粒子径０．６０μｍのシードラテックスを得た。次いで１ｍ^３オートクレーブ中に脱イオン水３５０．０ｋｇ、塩化ビニル単量体４００．０ｋｇ、２０重量％ドデシルベンゼンスルホン酸ナトリウム水溶液２．０ｋｇ、シードラテックスを塩化ビニル単量体に対して３．１重量％仕込み、この反応混合物の温度を６４℃にあげて重合を開始した。重合開始してから重合終了までの間、塩化ビニル単量体に対してドデシルベンゼンスルホン酸ナトリウム０．７重量部を連続的に添加した。重合時間３６０分後、重合圧が６４℃における塩化ビニル単量体の飽和蒸気圧から０．６５ＭＰａ降下した時に重合を停止し、未反応の塩化ビニル単量体を回収し接着助剤（塩化ビニルホモポリマーラテックス）を得た（ｐＨ７．３、平均粒子径１．４８μｍ）。

Comparative Example 1
A 1 m ³ autoclave was charged with 360.0 kg of deionized water, 300.0 kg of vinyl chloride monomer, 10.0 kg of lauroyl peroxide, 30.0 kg of 15 wt% aqueous sodium dodecylbenzenesulfonate and 1.5 kg of dodecyl mercaptan, The polymerization solution was circulated for 2 hours with a homogenizer and homogenized, and then the temperature was raised to 45 ° C. to initiate the polymerization reaction. After the pressure decreased, unreacted vinyl chloride monomer was recovered to obtain a seed latex having an average particle size of 0.60 μm. Next, in a 1 m ³ autoclave, 350.0 kg of deionized water, 400.0 kg of vinyl chloride monomer, 2.0 kg of 20 wt% sodium dodecylbenzenesulfonate aqueous solution, and 3.1 weight of seed latex with respect to the vinyl chloride monomer Polymerization was started by raising the temperature of the reaction mixture to 64 ° C. From the start of polymerization to the end of polymerization, 0.7 parts by weight of sodium dodecylbenzenesulfonate was continuously added to the vinyl chloride monomer. After a polymerization time of 360 minutes, the polymerization was stopped when the polymerization pressure dropped from the saturated vapor pressure of the vinyl chloride monomer at 64 ° C. by 0.65 MPa, and the unreacted vinyl chloride monomer was recovered and an adhesion assistant (vinyl chloride) (Homopolymer latex) was obtained (pH 7.3, average particle size 1.48 μm).

Comparative Example 2
As shown in Table 5, deionized water, 540.0 g of vinyl chloride monomer, and 60.0 g of acrylic acid monomer were charged into a 2.5 L autoclave in the same manner as in Example 1, and the temperature was raised to 66 ° C. Then, emulsion polymerization was started. The temperature was kept at 66 ° C., and 60 minutes after the start of polymerization, 50.0% sodium dodecylbenzenesulfonate aqueous solution 130.0 g and 5 wt% potassium laurate aqueous solution 2.4 g were continuously added over 290 minutes. After the pressure in the autoclave at 66 ° C. dropped to 0.65 MPa, unreacted vinyl chloride monomer and acrylic acid monomer were recovered to obtain an adhesion assistant (vinyl chloride / acrylic acid copolymer latex). (PH 2.2, average particle size 0.10 μm).

比較例３〜４
表５に示す通り、実施例１と同様の操作で２．５Ｌオートクレーブ中に脱イオン水、塩化ビニル単量体５４０.０ｇ、（メタ）アクリル酸アルキルエステル単量体としてアクリル酸単量体（比較例３）、アクリル酸ドデシル単量体（比較例４）６０.０ｇを各々仕込み、接着助剤（塩化ビニル／アクリル酸共重合体ラテックス、塩化ビニル／アクリル酸ドデシル共重合体ラテックス）を各々得た（ｐＨ及び平均粒子径を表５に示す）。

Comparative Examples 3-4
As shown in Table 5, in the same manner as in Example 1, deionized water, 540.0 g of vinyl chloride monomer, and acrylic acid monomer ((meth) acrylic acid alkyl ester monomer) in a 2.5 L autoclave. Comparative Example 3) and 60.0 g of dodecyl acrylate monomer (Comparative Example 4) were charged, respectively, and adhesion assistants (vinyl chloride / acrylic acid copolymer latex, vinyl chloride / dodecyl acrylate copolymer latex) Obtained (pH and average particle size are shown in Table 5).

Comparative Examples 5-6
As shown in Table 5, deionized water, 540.0 g of vinyl chloride monomer, and 60.0 g of butyl acrylate monomer were charged into a 2.5 L autoclave in the same manner as in Example 1, and 5 wt% dodecylbenzene. The amount of sodium sulfonate aqueous solution was changed to obtain adhesion aids (vinyl chloride / butyl acrylate copolymer latex) (Comparative Example 5: pH 6.5, average particle size 0.03 μm, Comparative Example 6: pH 6. 3, average particle size 1.54 μm).

Comparative Example 7
Adhesive aid (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) is added to 200.0 g of RFL solution corresponding to 100.0 parts by weight of RFL resin having the same composition as in Example 6 in solid content. Without adding RFLC solution, 4.3 g of VALQUABOND MDX equivalent to 2.1 parts by weight was placed in a 0.5 liter beaker, stirred with a magnetic stirrer for 20 minutes, and filtered with a 100-mesh wire mesh. Prepared. Tetron fibers were immersed in this treatment solution for 10 minutes to remove moisture at 140 ° C., and then baked at 240 ° C. for 2 minutes to obtain treated fibers. This treated fiber and a natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, which was evaluated in the same manner as in Example 6. The results are shown in Table 6. As is apparent from Table 6, the RFL adhesive treatment liquid containing no adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) is excellent in storage stability, but compared with Example 6, The initial adhesive strength and the adhesive strength after heat resistance deterioration were inferior.

比較例８
固形分にして、実施例６と同一組成のＲＦＬ樹脂１００.０重量部と比較例１の塩化ビニルホモポリマー２０.０重量部になるようにＲＦＬ液及び接着助剤（塩化ビニルホモポリマーラテックス）とバルカボンドＭＤＸ２．１重量部を加えたＲＦＬ接着剤処理液を調製し、テトロン繊維の処理を行い、この処理繊維と天然ゴム組成物を加硫接着し、ゴム組成物−繊維複合体を調製し、実施例６と同様の方法で評価を行った。その結果を表６に示す。表６から明らかなように、実施例６に比べ、比較例１を用いたＲＦＬ接着剤処理液の貯蔵安定性や、ゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力は劣っていた。

Comparative Example 8
The RFL solution and the adhesion assistant (vinyl chloride homopolymer latex) were adjusted so that the solid content was 100.0 parts by weight of the RFL resin having the same composition as in Example 6 and 20.0 parts by weight of the vinyl chloride homopolymer of Comparative Example 1. An RFL adhesive treatment solution containing 2.1 parts by weight of VALQUABOND MDX is prepared, the tetron fiber is treated, the treated fiber and the natural rubber composition are vulcanized and bonded, and a rubber composition-fiber composite is prepared. Evaluation was performed in the same manner as in Example 6. The results are shown in Table 6. As is clear from Table 6, compared to Example 6, the storage stability of the RFL adhesive treatment solution using Comparative Example 1, the initial adhesive strength of the rubber composition-fiber composite, and the adhesive strength after heat deterioration are It was inferior.

Comparative Example 9
The RFL solution and the adhesion assistant (salt chloride) were adjusted so that the solid content was 100.0 parts by weight of the RFL resin having the same composition as in Example 6 and 20.0 parts by weight of the vinyl chloride / acrylic acid copolymer of Comparative Example 2. Vinyl / acrylic acid copolymer latex) and 2.1 parts by weight of VALQUABOND MDX are prepared, a tetron fiber is treated, and the treated fiber and natural rubber composition are vulcanized and bonded to rubber. A composition-fiber composite was prepared and evaluated in the same manner as in Example 6. The results are shown in Table 6. As is clear from Table 6, the storage stability of the RFL adhesive treatment liquid using Comparative Example 2, the initial adhesive strength of the rubber composition-fiber composite, and the adhesive strength after heat deterioration compared to Example 6 are as follows. It was inferior.

Comparative Examples 10-11
The solid content was 100.0 parts by weight of RFL resin having the same composition as in Example 6, the vinyl chloride / acrylic acid copolymer in Comparative Example 3 and the vinyl chloride / dodecyl acrylate copolymer in Comparative Example 4 at 20. Two types of RFL adhesion, adding RFL liquid and adhesion aid (vinyl chloride / acrylic acid copolymer latex, vinyl chloride / dodecyl acrylate copolymer latex) and 2.1 parts by weight of VALQUABOND MDX to 0 parts by weight An agent treatment solution was prepared and the tetron fiber was treated. The treated fiber and the natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, which was evaluated in the same manner as in Example 6. . The results are shown in Table 6. As is clear from Table 6, Comparative Example 10 has good storage stability of the RFL adhesive treatment liquid, but compared with Examples 6 to 8, the initial adhesive strength of the rubber composition-fiber composite and after heat resistance deterioration Adhesion was poor. Comparative Example 11 was excellent in the initial adhesive strength of the rubber composition-fiber composite, but compared with Examples 6-8, the storage stability of the RFL adhesion treatment liquid and the rubber composition-fiber composite The adhesive strength after heat resistance deterioration was poor.

Comparative Examples 12-13
The RFL solution was adjusted so that the solid content was 100.0 parts by weight of RFL resin having the same composition as in Example 6 and the vinyl chloride / butyl acrylate copolymer of Comparative Examples 5 and 6 was 20.0 parts by weight. And two types of RFL adhesive treatment solutions containing adhesion aid (vinyl chloride / butyl acrylate copolymer latex) and Vulcabond MDX 2.1 parts by weight were prepared and treated with Tetron fiber. The composition was vulcanized and bonded to prepare a rubber composition-fiber composite and evaluated in the same manner as in Example 6. The results are shown in Table 6. As is clear from Table 6, Comparative Example 12 has good storage stability of the RFL adhesive treatment liquid, but compared with Examples 9 to 10, the initial adhesive strength of the rubber composition-fiber composite and after heat deterioration Adhesion was poor. Comparative Example 13 is inferior to Examples 9 to 10 in terms of storage stability of the RFL adhesion treatment liquid and adhesive strength after heat resistance deterioration of the rubber composition-fiber composite. The initial adhesive strength of the composition-fiber composite was poor.

Comparative Example 14
An RFL adhesive treatment liquid was prepared by adding 2.1 parts by weight of VALQUABOND MDX to an RFL liquid corresponding to 100.0 parts by weight of the RFL resin having the same composition as in Example 6. This was used to treat the tetron fiber, and the treated fiber and the SBR composition were vulcanized and bonded to prepare a rubber composition-fiber composite. Evaluation was performed in the same manner as in Example 6. The results are shown in Table 7. As is clear from Table 7, the storage stability of the RFL adhesive treatment solution was excellent, but compared with Example 11, the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat deterioration were inferior.

比較例１５
比較例１４で用いたＲＦＬ接着剤処理液を用い、ゴムをＳＢＲからＣＲに変更した以外は実施例６と同じ評価をテトロン繊維で行った。その結果を表７に示す。表７から明らかなように、ＲＦＬ接着剤処理液の貯蔵安定性は優れるが、実施例１２に比べ、ゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力が劣っていた。

Comparative Example 15
Using the RFL adhesive treatment solution used in Comparative Example 14, the same evaluation as in Example 6 was performed with Tetron fiber, except that the rubber was changed from SBR to CR. The results are shown in Table 7. As is clear from Table 7, the storage stability of the RFL adhesive treatment solution was excellent, but compared with Example 12, the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat degradation were inferior.

Comparative Example 16
An RFL adhesive treatment liquid corresponding to 100.0 parts by weight of RFL resin having the same composition as in Example 6 in terms of solid content was prepared. Tetron fibers were pretreated with Dismodule RE in the same manner as in Example 13, and the CSM composition-Tetron fiber composites were evaluated. The results are shown in Table 7. As is clear from Table 7, the storage stability of the RFL adhesive treatment solution was excellent, but the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat resistance deterioration were inferior to those of Example 13.

Comparative Example 17
RFL adhesive treatment solutions corresponding to 100.0 parts by weight of RFL resin having the same composition as in Examples 14 to 17 were prepared. Then, the nylon fiber was treated using this, and the treated fiber and the natural rubber composition were vulcanized and adhered, and evaluation was performed in the same manner as in Example 6. The results are shown in Table 8. As is clear from Table 8, the storage stability of the RFL adhesive treatment solution was excellent, but the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat degradation were inferior to those of Example 14.

比較例１８
比較例１７で用いたＲＦＬ接着剤処理液を用い、ゴムを天然ゴムからＳＢＲに変更した以外は実施例６と同じ評価をナイロン繊維で行った。その結果を表８に示す。表８から明らかなように、ＲＦＬ接着剤処理液の貯蔵安定性は優れるが、実施例１５に比べ、ゴム組成物−繊維複合体の初期接着力や耐熱劣化後の接着力が劣っていた。

Comparative Example 18
The same evaluation as in Example 6 was performed with nylon fibers, except that the RFL adhesive treatment liquid used in Comparative Example 17 was used and the rubber was changed from natural rubber to SBR. The results are shown in Table 8. As is clear from Table 8, the storage stability of the RFL adhesive treatment solution was excellent, but the initial adhesive strength and the adhesive strength after heat deterioration of the rubber composition-fiber composite were inferior to those of Example 15.

Comparative Example 19
The same evaluation as in Example 6 was performed with nylon fibers except that the RFL adhesive treatment liquid used in Comparative Example 17 was used and the rubber was changed from natural rubber to CR. The results are shown in Table 8. As is clear from Table 8, the storage stability of the RFL adhesive treatment solution was excellent, but the initial adhesive strength and the adhesive strength after heat deterioration of the rubber composition-fiber composite were inferior to those of Example 16.

Comparative Example 20
The same evaluation as in Example 6 was performed with nylon fibers except that the RFL adhesive treatment solution used in Comparative Example 17 was used and the rubber was changed from natural rubber to CSM. The results are shown in Table 8. As is clear from Table 8, the storage stability of the RFL adhesive treatment solution was excellent, but the initial adhesive strength of the rubber composition-fiber composite and the adhesive strength after heat resistance deterioration were inferior to those of Example 17.

Comparative Example 21
With respect to 200.0 g of RFL solution corresponding to 100.0 parts by weight of RFL resin having the same composition as in Example 6 in terms of solid content, an adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) was added. Without addition, 4.3 g of VALQUABOND MDX equivalent to 2.1 parts by weight with respect to the RFL solution was placed in a 0.5 liter beaker, stirred for 20 minutes with a magnetic stirrer, and then filtered through a 100-mesh wire mesh. Was prepared. In this treatment liquid, glass fibers were immersed for 10 minutes to obtain treated fibers from which moisture was removed at 140 ° C. This treated fiber and a natural rubber composition were vulcanized and bonded to prepare a rubber composition-fiber composite, which was evaluated in the same manner as in Example 6. The results are shown in Table 9. As is apparent from Table 9, the RFL adhesive treatment liquid containing no adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) is excellent in storage stability but has an initial adhesive force and heat resistance deterioration. Later adhesion was poor.

比較例２２
ゴムを天然ゴムからＳＢＲに変更した以外は比較例２１と同じ評価をガラス繊維で行った。その結果を表９に示す。表９から明らかなように、接着助剤（塩化ビニル−（メタ）アクリル酸アルキルエステル共重合体ラテックス）を含有しないＲＦＬ接着剤処理液は、貯蔵安定性に優れるものの、初期接着力や耐熱劣化後の接着力は劣っていた。

Comparative Example 22
The same evaluation as Comparative Example 21 was performed with glass fiber except that the rubber was changed from natural rubber to SBR. The results are shown in Table 9. As is apparent from Table 9, the RFL adhesive treatment liquid containing no adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) is excellent in storage stability but has an initial adhesive force and heat resistance deterioration. Later adhesion was poor.

Comparative Example 23
The same evaluation as Comparative Example 21 was performed with glass fiber except that the rubber was changed from natural rubber to CR. The results are shown in Table 9. As is apparent from Table 9, the RFL adhesive treatment liquid that does not contain an adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester) is excellent in storage stability but has an initial adhesive force and an adhesive force after heat deterioration. Was inferior.

Comparative Example 24
The same evaluation as Comparative Example 21 was performed with glass fiber except that the rubber was changed from natural rubber to CSM. The results are shown in Table 9. As is apparent from Table 9, the RFL adhesive treatment liquid containing no adhesion assistant (vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex) is excellent in storage stability but has an initial adhesive force and heat resistance deterioration. Later adhesion was poor.

  The rubber composition-fiber composite of the present invention uses the RFL adhesive treatment liquid of the present invention using the adhesion aid of the present invention, so that the initial adhesive force between the rubber composition and the fiber and adhesion after heat deterioration Since the rubber composition-fiber composite molded product of the present invention is excellent in strength, it is used for tires such as automobile tires, motorcycle / bicycle tires, solid tires for industrial vehicles, V belts, toothed belts, conveyor belts. , Various belts such as automobile belts and industrial belts such as flat belts for power transmission, rubber hoses for automobiles, industrial rubber hoses, air vanes for trucks and buses, air vanes for automobiles, air vanes for railway vehicles, industrial machinery Used for a wide range of applications such as air blades such as air blades, civil engineering and construction sheets, and daily commodities for rubber footwear.

Claims (6)

A vinyl chloride- (meth) acrylic acid alkyl ester copolymer containing vinyl chloride and an alkyl (meth) acrylate represented by the following general formula (1), having a pH of 3 to 8 and an average particle size of 0.05 to 1.0 μm An adhesion aid comprising a combined latex.

(In the formula, R ₁ represents hydrogen or a methyl group, and n represents an integer of 1 to 10.) The adhesion promoter according to claim 1, wherein the vinyl chloride- (meth) acrylic acid alkyl ester copolymer latex contains an organic compound having a sulfonate salt or a sulfate ester salt and a higher fatty acid salt. 3. An RFL adhesive treatment liquid comprising the adhesion assistant according to claim 1 or 2, and an RFL liquid containing an aqueous solution of resorcin and formalin condensate and a rubber latex. The adhesion aid according to claim 1 or claim 2, resorcin and RFL adhesive according to claim 3, wherein the mixing and dispersing become possible in the RFL solution comprising an aqueous solution and a rubber latex formalin condensate Treatment liquid. The RFL adhesive treatment liquid according to claim 3 or claim 4 impregnated into the fiber, followed by drying and formed by processing fiber and the rubber composition The rubber composition is characterized by being obtained by vulcanizing the - fiber composites . The RFL adhesive treatment liquid according to claim 3 or claim 4 impregnated into the fiber, and then dried to become processed fiber, a rubber composition obtained by vulcanizing the rubber composition - by molding fiber composite A molded article of a rubber composition-fiber composite characterized by comprising: